Process for Making a Boric Acid Free Flux

ABSTRACT

The invention described herein pertains generally to a process for making boric acid free flux compositions in which boric acid and/or borax is substituted with a molar equivalent amount of potassium tetraborate tetrahydrate. In some embodiments, a phthalocyanine pigment is used to affect a color change at activation temperature.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of pending U.S. utility patentapplication Ser. No. 14/211,125, filed on Mar. 14, 2014, which is acontinuation-in-part of U.S. utility patent application Ser. No.13/838,485, filed on Mar. 15, 2013, which issued as U.S. Pat. No.9,174,310 on Nov. 3, 2015, each of which is fully incorporated herein byreference.

TECHNICAL FIELD

The invention described herein pertains generally to boric acid freebrazing flux compositions.

BACKGROUND

In general, brazing fluxes remove oxides and contaminants from basematerials to ensure good quality brazed joints. The choice of fluxdepends on the base material to be used, in addition to the filler metaltypes, heat source, and application method. Brazing joins similar anddissimilar materials by heating them in the presence of filler metalhaving a liquidus above 425° C.-450° C. (˜800° F.-840° F.) and below thesolidus of the base material. During brazing, filler metal flows betweenfitted surfaces of the joint by capillary action. The minimumtemperature on the surface of the component to be brazed at which saidprocess takes place undisturbed is the so-called working temperature. Itis a characteristic quantity for the filler metal in question. Fillermetals can be alloys or pure metals. In general, the heat from brazingis less damaging than the heat from welding. Additionally, brazed jointstypically have higher strength than soft-soldered joints. The choice offlux plays an important role in most all brazing processes, and the useof an incorrect flux can compromise joint quality.

In order to be able to form a bond with the base metal, the moltenfiller metal must come into direct contact with the base metal. Oxidelayers of the kind present on any engineering metal surface must thus beloosened first and removed. If brazing takes place in the air, this isachieved by covering the brazing site with fluxes in the melt flow inwhich the oxides dissolve, are reduced or decompose at and above theactive temperature of the flux.

When heated, fluxes dissolve surface oxides and protect the cleanedsurfaces from re-oxidation, transfer heat from the heat source to thejoint, and remove oxidation products, allowing filler metal to contactand wet the base materials. Brazing fluxes, pastes or powders, activateat temperatures below those needed to melt filler metals. Because fluxesmust be in close contact with the joint surfaces, they are liquid orgaseous at brazing temperatures. They remove only surface oxides andtarnish. Other contaminants must be removed either mechanically orchemically before brazing.

Fluxes are typically classified by form (powder, liquid, or paste), basematerials and filler metals they can be used with, heat source,application method, and active temperature range. Silver brazing fluxescontain boric acid and potassium borates, combined with complexpotassium fluoroborate and fluoride compounds. Fluorides, up to 40% influx content, give these fluxes their characteristically low meltingpoints and high capacity for dissolving metal oxides. High temperaturefluxes, based on boric acid and alkaline borates, sometimes, containsmall additions of elemental boron or silicon dioxide to increaseactivity and protection.

The melting point and the effective temperature of the fluxes must bematched to the working temperature of the brazing filler metal used,whereby the flux should melt at about 50-100° C. below the workingtemperature of the filler metal used and become fully effective fromthis temperature onwards. Moreover, the molten flux should form a dense,uniform coating on the workpiece which remains intact at the requiredbrazing temperature and for the duration of the brazing period.

Assuming pure metal surfaces, the liquid filler metal is able to spreadin a thin layer on the base metal surface, wetting it. The filler metaladheres to the base metal surface by a slight alloying of the base andfiller metals. The filler metal spreads out over the joint surface and,after solidifying, forms a loadable joint with the base metal.

Brazing fluxes are composed substantially of salt mixtures which, in themolten state, are capable of dissolving metal oxides. These fluxes aresubstantially inorganic boron compounds such as, in particular, alkaliborates and fluoroborates, including boric acid, and halides such as, inparticular, an alkali halide; e.g. alkali fluorides.

Per the Regulation (EC) No 1272/2008 of the European Parliament and ofthe Council on classification, labeling and packaging of substances andmixtures” boric acid (a component of most brazing fluxes), is classifiedas a reproductive toxin in the European Union. This requires speciallabeling, leading to an effort on the part of consumers to look forboric acid free alternatives. Suitable boric acid free brazing fluxesmust be developed to maintain market share and meet consumer demand.

At least one aspect of the invention resides in the superior ability toachieve desirable flux characteristics without the presence of boricacid (H₃BO₃) or borax (NaB₄O₅(OH)₄.H₂O) in the flux.

SUMMARY

The invention describes various flux compositions which do not containboric acid, and which optionally include a color change pigment atactivation temperature, e.g., a phthalocyanine pigment.

In one embodiment, a boric acid free paste flux composition is describedthat contains: water; potassium bifluoride (KHF₂); fumed silica (SiO₂);potassium tetraborate (K₂B₄O₇.4H₂O); and potassium fluoroborate (KBF₄).

For high temperature applications, the boric acid free paste fluxcomposition often contains boron.

For low temperature applications, one embodiment of the boric acid freepaste flux composition contains on a weight percent basis: water(balance to total 100%); a wetting agent, preferably UDYLITE 62(0.1-1%); potassium bifluoride (KHF₂) (12-16%); fumed silica (SiO₂)(0.1-4%); potassium tetraborate tetrahydrate (K₂B₄O₇.4H₂O) (26-35%);potassium fluoroborate (KBF₄) (26-35%); and pigment (phthalocyanine)(0.1-2%).

For high temperature applications, another embodiment of the boric acidfree paste flux composition contains on a weight percent basis: water(balance to total 100%); wetting agent, preferably UDYLITE 62 (0.1-1%);potassium bifluoride (KHF₂) (12-16%); fumed silica (SiO₂) (0.1-4%);potassium tetraborate tetrahydrate (K₂B₄O₇.4H₂O) (26-35%); potassiumfluoroborate (KBF₄) (26-35%); and boron (0.1-2%).

For powder applications, the boric acid free powder flux compositionincludes: potassium tetraborate (K₂B₄O₇.4H₂O); potassium fluorosilicate(K₂SiF₆); and potassium fluoroborate (KBF₄).

For high temperature applications, the boric acid free powder flux willcontain boron.

For high temperature applications, one embodiment of the boric acid freepowder flux composition will include on a weight basis: potassiumtetraborate tetrahydrate (K₂B₄O₇.4H₂O) (44-54%); potassiumfluorosilicate (K₂SiF₆) (1-3%); potassium fluoroborate (KBF₄) (44-54%);and boron (0.1-2%).

For low temperature applications, another embodiment of the boric acidfree powder flux composition will include on a weight basis: potassiumtetraborate tetrahydrate (K₂B₄O₇.4H₂O) (44-54%); potassiumfluorosilicate (K₂SiF₆) (1-3%); potassium fluoroborate (KBF₄) (44-54%);and pigment (phthalocyanine) (0.1-2%).

The invention includes a process of making a boric acid free flux whichcomprises the step of replacing boric acid present in a boric acidcontaining flux with a substantially similar molar amount of potassiumtetraborate tetrahydrate (K₂B₄O₇.4H₂O). The process optionally alsoincludes the step of adding a phthalocyanine pigment effects a colorchange at an activation temperature of said flux.

The invention further includes a process of making a boric acid freeflux which comprises the step of: replacing borax present in a boraxcontaining flux with a substantially similar molar amount of potassiumtetraborate tetrahydrate (K₂B₄O₇.4H₂O). The process optionally alsoincludes the step of adding a phthalocyanine pigment effects a colorchange at an activation temperature of said flux.

These and other objects of this invention will be evident when viewed inlight of the detailed description and appended claims.

DETAILED DESCRIPTION

The best mode for carrying out the invention will now be described forthe purposes of illustrating the best mode known to the applicant at thetime of the filing of this invention. The examples are illustrative onlyand not meant to limit the invention, as measured by the scope andspirit of the claims.

As used herein, the term “approximately” or “about” means within thestated ranges with a tolerance of 10%.

The present brazing flux composition is boric acid free, provides goodwetting characteristics and changes color from a color in the visiblespectrum to clear at activation temperature.

The invention will now be described in a series of non-limiting, butillustrative examples.

Boric acid has a melting temperature of approximately 336° F. (169° C.)and melts early during heating in the brazing process. This allows boricacid brazing fluxes to begin melting at low temperatures, well beforebrazing temperature is reached, thereby protecting the faying surfacesfrom further oxidation. Additionally, this low melting temperature,coupled a boiling/dehydration temperature of approximately 532° F. (300°C.) helps to create brazing fluxes that hot rod well, that is to saythat the flux will melt, then subsequently freeze, adhering to heatedbrazing rod. By the time boric acid reaches 842° F. (450° C.) itcompletely dehydrates (or decomposes releasing H₂O) leaving borontrioxide, which protects the base and filler metal surfaces throughoutthe remaining brazing process. Replacing boric acid in a brazing fluxrequires the substitution of the boric acid with one or more compoundsthat can approximately duplicate the above properties.

Several compounds have attributes which would lend themselves to a boricacid replacement. These options would include, at a minimum: acombination of potassium carbonate and di-ammonium phosphate; andammonium fluoroborate or ammonium fluorosilicate and potassiumtetraborate tetrahydrate. In general, sodium salts were not consideredas a likely replacement due in large part to the “sodium glare”encountered when heated to brazing temperatures. In addition,sodium-borate salts were further removed from consideration because theyare specified in EU “regulation (EC) No 1272/2008 of the EuropeanParliament and of the Council on classification, labeling and packagingof substances and mixtures” as having the same restrictions and boricacid.

Potassium carbonate offers protection at temperatures exceeding 1600° F.(871° C.); and combining potassium carbonate with diammonium phosphate(DAP) would allow protection from oxidation above 302° F. (150° C.).However, while meeting some of the replacement criteria, it wasdetermined that this combination was not practical for a dry powderedflux due to the deliquescence of potassium carbonate, the tendency ofthe flux to absorb moisture. The high dissociation partial pressure ofammonia from DAP require that the flux remain in a tightly sealedcontainer when it is not in use, to preserve flux chemical and physicalproperties. The release of ammonia is also an issue with the ammoniafluoroborate and fluorosilicate; the release of ammonia is exacerbatedwhen the paste flux is made due to the ready dissociation of ammoniafrom its anionic counterparts in an aqueous solution, though water gainis not an issue. Although these flux formulations yield an adequateperformance, better alternatives were pursued based on at least twofactors: (1) the unpleasant ammonia fume, from flux application toheating; and (2) the probable change in flux properties throughhygroscopic update over time.

Potassium tetraborate is also found in brazing fluxes. It readilydissolves metallic (not refractory) oxides at high temperature almost aswell as potassium pentaborate (also another replacement option) at afraction of the cost. It was selected as an option to consider in thereplacement of boric acid. Anhydrous potassium tetraborate alone doesnot melt until 1500° F. (816° C.) and is hygroscopic, converting to thetetrahydrate with prolonged exposure to humidity. Hydration of powderedanhydrous potassium tetraborate fluxes causes an uncontrolled change influx properties over time and imposes unnecessary conditions and/orprocessing during manufacture. Hydration is an exothermic process thatcauses manufacturing concerns. While anhydrous powdered potassiumtetraborate flux does perform adequately, the flux does not melt untilthe faying surface is hot enough to form additional oxides, which willsubsequently need to be removed. Additionally this flux will not “hotrod” well due to the high melting temperature. For all of these reasonspotassium tetraborate tetrahydrate was chosen as a preferred replacementover anhydrous potassium tetraborate as a boric acid substitute.

The invention will now be described by a series of non-limitingexamples.

EXAMPLE #1

In one embodiment of the invention, a black high temperature paste fluxis described, the composition of which includes a mixture of water,potassium tetraborate tetrahydrate, potassium bifluoride, boron, UDYLITE(Udylite 62 is a product of Enthone®, 350 Frontage Road, West Haven,Conn.) and fumed silica in the following weight percentages.

TABLE I High Temperature Boric Acid Free Paste Flux Weight ComponentPercentage water balance wetting agent 0.1-1% wetting agent/surfactant(UDYLITE 62) potassium bifluoride 12-16%  etchant/clean base metalsurface (KHF₂) fumed silica (SiO₂) 0.1-4% emulsifying agent/plasticizerpotassium tetraborate 26-35%  dissolve metallic oxides and protecttetrahydrate brazing surface from oxidation (K₂B₄O₇•4H₂O) potassiumfluoroborate 26-35%  dissolve metallic oxides and halides (KBF₄) andprotect brazing surface from oxidation boron 0.1-2% protect surface fromoxidation at high brazing temperatures Total   100% (all components willtotal 100%)

EXAMPLE #2

In another embodiment of the invention, a low temperature boric acidfree paste flux will include a mixture of water, potassium bifluoride,potassium tetraborate tetrahydrate, potassium fluoroborate, pigment,UDYLITE and fumed silica in the following weight percentages.

TABLE II Low Temperature Boric Acid Free Paste Flux Weight ComponentPercentage water balance wetting agent 0.1-1% wetting agent/surfactant(UDYLITE 62) potassium bifluoride 12-16%  etchant/clean base metalsurface (KHF₂) fumed silica (SiO₂) 0.1-4% emulsifying agent/plasticizerpotassium tetraborate 26-35%  dissolve metallic oxides and protecttetrahydrate brazing surface from oxidation (K₂B₄O₇•4H₂O) potassiumfluoroborate 26-35%  dissolve metallic oxides and halides (KBF₄) andprotect brazing surface from oxidation pigment (phthalo- 0.1-2% activetemperature indicator cyanine) Total   100% (all components will total100%)

Copper Phthalocyanine Green No. 7 was employed in several compositionsas a visual indicator of activation temperature. It decomposes in therange of temperature form 1022° F. (550° C.) to 1650° F. (900° C.),depending on the level of accessible oxidizing agents. Testing revealedreliable correlation between the color change of the low temperature(green) brazing fluxes from green to clear and brazing temperature, atthe faying surfaces. Furthermore this color change did not appear to bedependent on the level of pigmentation.

EXAMPLE #3

In another embodiment of the invention, a high temperature boric acidfree powder flux will include a mixture of potassium tetraboratetetrahydrate, potassium fluorosilicate, potassium fluoroborate and boronin the following weight percentages.

TABLE III High Temperature Boric Acid Free Powder Flux Weight ComponentPercentage potassium tetraborate 44-54% dissolve metallic oxides andprotect tetrahydrate brazing surface from oxidation (K₂B₄O₇•4H₂O)potassium fluoro-  1-3% wetting agent/surfactant silicate (K₂SiF₆)potassium fluoroborate 44-54% dissolve metallic oxides and halides(KBF₄) and protect brazing surface from oxidation boron  0.1-2% protectsurface from oxidation at high brazing temperatures Total  100% (allcomponents will total 100%)

EXAMPLE #4

In another embodiment of the invention, a low temperature boric acidfree powder flux will include a mixture of potassium tetraboratetetrahydrate, potassium fluorosilicate, potassium fluoroborate and apigment in the following weight percentages.

TABLE IV Low Temperature Boric Acid Free Powder Flux Weight ComponentPercentage potassium tetraborate 44-54% dissolve metallic oxides andprotect tetrahydrate brazing surface from oxidation (K₂B₄O₇•4H₂O)potassium fluoro-  1-3% wetting agent/surfactant silicate (K₂SiF₆)potassium fluoroborate 44-54% dissolve metallic oxides and halides(KBF₄) and protect brazing surface from oxidation pigment (phthalo- 0.1-2% active temperature indicator cyanine 500-600° C.) Total  100%(all components will total 100%)

As described above, the phthalocyanine pigment is an aromaticmacrocyclic compound that forms coordination complexes with manyelements of the periodic table. These complexes are intensely coloredwhich facilitates the color transformation at temperatures employed inthe reaction. As described above, the phthalocyanine pigment is anaromatic macrocyclic compound that forms coordination complexes withmany elements of the periodic table. These complexes are intenselycolored which facilitates the color transformation at temperaturesemployed in the reaction from colored in the visible spectrum toessentially colorless at temperature. The phthalocyanine macrocycliccompound is illustrated below, and wherein a metallic ion would becoordination bonded to the nitrogen atoms, typically within the5-membered rings.

The above compositions are useful for the brazing of metallic materialsbased on copper, silver, nickel and iron based alloys. Without beingheld to any one theory or mechanism of operation, the flux is used toremove the oxide layer and enable the wetting of the base materials. Theactivated flux creates a layer on the workpiece and removes any surfaceoxides. The color change at activation temperature is a distinctcharacteristic not seen when compared to fluxes commercially availablefor purchase.

Compositions and combinations of the above fluxes were tested and metall AWS A5.31M/A5.31:2012 testing standards for water content, particle,adhesion, fluidity, fluxing action, flow, life and viscosity.

The boric acid free fluxes described in Tables I-IV deliver excellentperformance, standing on their own as brazing fluxes. As discussedbelow, the boric acid free fluxes deliver results often superior tocommercially available standard fluxes that are not boric acid free.

In addition, the following tests were performed on an additional seriesof fluxes synthesized using the compositions identified in Tables 1-6with the performance criteria identified and defined below beingcharacterized in Tables 1a-6a.

Oxide Removal

All of the boric acid free fluxes dissolved all oxides from the basemetal surface.

Activation Range

All of the boric acid free fluxes are fully active, removing oxides,throughout the range of 1050° F.-1600° F. (566° C.-871° C.) and 1050°F.-1800° F. (566° C.-982° C.), for the low temperature (green) flux andthe high temperature flux (black) respectively.

Hot Rodding

“Hot Rodding” is the coating of a piece of brazing rod (filler metal) bydipping a hot end into a powdered flux. This is applicable to powderfluxes only. Both powder fluxes “hot rodded” extremely well.

Flux Flowability in Activation Range

A flowability test was performed per AWS A5.31M/A5.31:2012. Flowabilitywas good for both the boric acid free powders and the pastes.

Brazing Odor and Fumes

There was very little objectionable odor and fumes throughout thebrazing process for all of the boric acid free fluxes.

Activation Indicator

The pigmented fluxes of Tables 2 & 4 were the only fluxes that had avisual indicator of activation temperature actually tested.

In judging the performance of brazing flux formulations seven criteriawere chosen:

-   -   (1) Hot Rod—The ability of a powder brazing flux to adhere to a        hot brazing rod/wire.    -   (2) Flux Flow—How well the molten flux spreads, or “wets out”,        across the heated surface of the base-metal(s)—more        specifically, how well the molten flux flows along the brazing        joint capillary and the immediately adjacent faying surfaces;    -   (3) Metal Flow—Metal flow is an arbitrary measure of the brazing        flux's ability to lower the surface tension of the molten filler        metal at the base-metal surface—it is in general measured by how        well the molten filler metal spreads, or “wets out”, across the        heated surface of the base-metal(s)—more specifically, how well        the molten filler metal flows along the brazing joint capillary        and the immediately adjacent faying surfaces;    -   (4) Acrid Odor—The quantity of fumes and smoke emitted and how        irritating, sharp or pungent they are;    -   (5) Flux Composition—The homogeneity and ease of application;    -   (6) Flux Residue—The ease with which flux residue is removed;        and    -   (7) Hot Clean—The ease with which flux residue is removed using        hot water alone.

Each criterion is evaluated for the flux formulation as having asubjective value between one and five, where 1 (one) is “not desirable”and 5 (five) is “desirable”.

In the following examples, testing was performed on eight powdered andthree paste flux test formulations of varying components and/or combinedin varying ratios. Of these formulations six contained boric acid toestablish several benchmarks. SSP-4 was chosen as our baseline forpowdered flux (Tables 1 & 1a) and SSWF as the baseline for the pasteflux (Tables 2 & 2a). None of the initial testing was forboron-containing (high temperature) fluxes. The assumption was made thata successful low temperature flux can be used as a basis for a hightemperature flux. Experience with prior art compositions bear this out.Furthermore, the green phthalocyanine pigment was not included in thefunctional tests of the low temperature fluxes, as it is present inlevels deemed too low to be of any significance to the performance ofthe flux, other than to provide visual indication to the operator.

Initial Powder Fluxes

TABLE 1 Composition (% mass) Test No NH₄BF₄ (NH₄)₂SiF₆ H₃BO₃ C₆H₈O₇K₂SiF₆ (NH₄)₂PO₄ K₂CO₃ KBF₄ KF K₂B₄O₇•4H₂O SSP-1 — — — — 22  5  9 64 — —SSP1-a — — — — 21  6 10 63 — — SSP1-b — — — — 22 12 13 53 — — SSP-f — — 5 22 — —  9 64 — — SSP-16 — 10 — — 30 10 20 — 30 — SSP-28 10 10 — — — —— 60 — 20 SSP-6 — — 15  5 20 — 10 50 — — SSP-4 — — 20 — 10 — 10 50 — —

TABLE 1a Base Hot Flux Metal Acrid Flux Flux Hot Test No Metal Rod FlowFlow Odor Comp Residue Clean SSP-1 Copper 1 4 3 2 5 4 5 Stainless 1 3 32 5 4 5 SSP1-a Copper 1 3 3 2 5 4 5 Stainless 1 3 3 2 5 4 5 SSP1-bCopper 1 3 4 1 4 3 4 Stainless 1 3 3 2 4 3 4 SSP-f Copper 2 3 3 2 3 3 5Stainless 2 3 4 2 3 3 4 SSP-16 Copper 1 4 4 4 5 5 5 Stainless 1 4 4 4 55 5 SSP-28 Copper 5 4 4 4 4 4 4 Stainless 5 4 4 4 4 4 4 SSP-6 Copper 3 53 2 5 4 5 Stainless 3 5 3 2 5 4 5 SSP-4 Copper 4 5 3 3 5 4 5 Stainless 45 3 3 5 4 5

Initial Paste Fluxes

TABLE 2 Composition (% mass) Udylite Test Copper No H₃BO₃ Wetting(NH₄)₂PO₄ KHF₂ K₂CO₃ KBF₄ KF Water SSP- 10 20 10 10 20 30 — Bal- 11 anceSSP- 20 20 10 10 20 — 20 Bal- 12 ance SSWF 41 0.03 — 18 — — 18 Bal- ance

TABLE 2a Base Hot Flux Metal Acrid Flux Flux Hot Test No Metal Rod FlowFlow Odor Comp Residue Clean SSP-11 Copper N/A 4 3 3 5 4 5 Stainless N/A4 3 3 5 4 5 SSP-12 Copper N/A 5 3 2 5 4 5 Stainless N/A 5 3 2 5 4 5 SSWFCopper N/A 5 3 4 5 4 5 Stainless N/A 5 3 4 5 4 5

Potassium tetraborate is a common component in brazing fluxes. Itreadily dissolves metallic (not refractory) oxides at high temperature;this makes it a natural consideration for replacement of boric acid; forthese reasons it was actually the chemical of first choice. Anhydrouspotassium tetraborate alone does not melt until 1500° F. (816° C.) andis hygroscopic, converting to the tetrahydrate with prolonged exposureto humidity. Hydration of powdered anhydrous potassium tetraboratefluxes causes an uncontrolled change in flux properties over time andimposes unnecessary conditions and/or processing during manufacture.Hydration is an exothermic process that causes manufacturing concerns.While anhydrous powdered potassium tetraborate flux does performadequately, the flux does not melt until the faying surface is hotenough to form some additional oxides, which will subsequently need tobe removed; additionally this flux will not “hot rod” well due to thehigh melting temperature. For these reasons potassium tetraboratetetrahydrate was chosen as a preferred embodiment over anhydrouspotassium tetraborate. Boric acid in both the powder and paste fluxeswas replaced with potassium tetraborate tetrahydrate. This replacementwas approximately a 1:1 molar ratio of borate content for both fluxesinitially, and then adjusted against the wetting agent(s) to achieve theoptimal performance.

Testing of Low Temperature (Green) Powder Boric Acid Free FluxFormulations

TABLE 3 Composition (% mass) Test No K₂SiF₆ KBF₄ K₂B₄O₇•4H₂O SSP-2 18 5725 SSP2-a 18 52 30 SSP2-b 20 40 40 SSP2-c 14 43 43 SSP2-d 10 45 45SSP2-e 8 46 46 SSP2-f 6 47 47 SSP2-g 2 49 49

TABLE 3a Base Hot Flux Metal Acrid Flux Flux Hot Test No Metal Rod FlowFlow Odor Comp Residue Clean SSP-2 Copper 2 4 4 2 5 4 5 Stainless 2 3 32 5 4 5 SSP2-a Copper 2 4 4 2 5 4 5 Stainless 2 3 3 2 5 4 5 SSP2-bCopper 2 4 4 2 5 4 5 Stainless 2 3 3 2 5 4 5 SSP2-c Copper 2 4 4 2 5 4 5Stainless 2 3 3 2 5 4 5 SSP2-d Copper 3 4 4 2 5 4 5 Stainless 3 3 4 2 54 5 SSP2-e Copper 3 4 4 3 5 4 5 Stainless 3 3 4 3 5 4 5 SSP2-f Copper 44 5 4 5 4 5 Stainless 4 4 4 4 5 4 5 SSP2-g Copper 5 5 5 4 5 4 5Stainless 5 5 5 4 5 4 5

Testing of High Temperature (Black) Powder Boric Acid Free FluxFormulations

TABLE 4 Composition (% mass) Test No Boron K₂SiF₆ KBF₄ K₂B₄O₇•4H₂OSSP2-h 5 5 50 40 SSP2-i 4 6 48 42 SSP-j 3 3 46 46 SSP-k 2 3 47 47 SSP-l2 3 48 48 SSP-m 1 3 48 48

TABLE 4a Base Hot Flux Metal Acrid Flux Flux Hot Test No Metal Rod FlowFlow Odor Comp Residue Clean SSP2-h Copper 1 2 3 3 5 3 5 Stainless 1 2 33 5 2 4 SSP2-i Copper 2 2 3 3 5 3 5 Stainless 2 2 3 3 5 2 4 SSP-j Copper3 2 3 3 5 3 5 Stainless 3 2 4 3 5 3 5 SSP-k Copper 3 3 3 3 5 4 5Stainless 3 3 4 3 5 3 5 SSP-l Copper 4 4 4 4 5 4 5 Stainless 4 4 4 4 5 45 SSP-m Copper 5 5 5 4 5 4 5 Stainless 5 5 5 4 5 4 5

Testing of Low Temperature (Green) Paste Boric Acid Free FluxFormulations

TABLE 5 Composition (% mass) Udylite Fumed Copper Test No SiO₂ WettingKHF₂ KBF₄ K₂B₄O₇•4H₂O Water SSP-48 2 1 23 23 28 Balance SSP48-A 2 1 2023 30 Balance SSP48-B 1 0.75 15 30 31 Balance SSP-C 1 0.05 15 32 32Balance SSP-D 1 0.5 14 32 32 Balance

TABLE 5a Base Hot Flux Metal Acrid Flux Flux Hot Test No Metal Rod FlowFlow Odor Comp Residue Clean SSP-48 Copper N/A 2 3 2 4 4 3 Stainless N/A2 2 2 4 4 3 SSP48-a Copper N/A 3 3 2 4 4 4 Stainless N/A 2 3 2 4 4 4SSP48-b Copper N/A 3 3 2 4 4 4 Stainless N/A 3 3 2 4 4 4 SSP-c CopperN/A 4 4 3 4 4 5 Stainless N/A 4 3 3 4 4 5 SSP-d Copper N/A 5 5 4 5 4 5Stainless N/A 5 5 4 5 4 5

Testing of High Temperature (Black) Paste Boric Acid Free FluxFormulations

TABLE 6 Composition (% mass) Udylite Test Fumed Copper No Boron SiO₂Wetting KHF₂ KBF₄ K₂B₄O₇•4H₂O Water SSP- 4 2 2 25 38 28 Bal- 50 anceSSP50- 3 2 2 23 36 29 Bal- a ance SSP50- 2 1 1 17 35 30 Bal- b anceSSP50- 1 1 0.75 15 33 31 Bal- c ance SSP50- 1 1 0.5 14 32 32 Bal- d ance

TABLE 6a Base Hot Flux Metal Acrid Flux Flux Hot Test No Metal Rod FlowFlow Odor Comp Residue Clean SSP-50 Copper N/A 3 3 2 4 4 4 Stainless N/A2 3 2 4 4 4 SSP50-a Copper N/A 3 3 3 4 4 4 Stainless N/A 3 3 3 4 4 4SSP50-b Copper N/A 4 4 3 4 4 5 Stainless N/A 3 4 3 4 4 4 SSP50-c CopperN/A 4 5 4 5 4 5 Stainless N/A 4 4 4 5 4 5 SSP50-d Copper N/A 5 5 4 5 4 5Stainless N/A 5 5 4 5 4 5

The invention has been described with reference to preferred andalternate embodiments. Obviously, modifications and alterations willoccur to others upon the reading and understanding of the specification.It is intended to include all such modifications and alterations insofaras they come within the scope of the appended claims or the equivalentsthereof.

What is claimed is:
 1. A process of making a boric acid free flux, whichcomprises the step of: replacing boric acid present in a boric acidcontaining flux with a substantially similar molar amount of potassiumtetraborate tetrahydrate (K₂B₄O₇.4H₂O).
 2. The process of claim 1further comprising the step of: adding a phthalocyanine pigment toaffect a color change at an activation temperature of said flux.
 3. Aprocess of making a boric acid free flux, which comprises the step of:replacing borax present in a borax containing flux with a substantiallysimilar molar amount of potassium tetraborate tetrahydrate(K₂B₄O₇.4H₂O).
 4. The process of claim 3 further comprising the step of:adding a phthalocyanine pigment to affect a color change at anactivation temperature of said flux.
 5. A process of making a boric acidfree flux composition, which comprises the step of: combining water,potassium bifluoride (KHF₂), fumed silica (SiO₂), potassium tetraborate(K₂B₄O₇.4H₂O); and potassium fluoroborate (KBF₄).
 6. The process ofclaim 5 further comprising the step of: combining the boric acid freeflux composition with boron.
 7. The process of claim 5 furthercomprising the step of: combining the boric acid free flux compositionwith a wetting agent.
 8. The process of claim 5 further comprising thestep of: combining the boric acid free flux composition with aphthalocyanine pigment, a wetting agent, and boron.
 9. The process ofclaim 5 further comprising the step of: combining the boric acid freeflux composition with a phthalocyanine pigment and a wetting agent;wherein the composition comprises approximately by weight percent, saidcomposition added in an amount totaling 100%: water balance; wettingagent 0.1-1%; potassium bifluoride (KHF₂) 12-16%;  fumed silica (SiO₂)0.1-4%; potassium tetraborate tetrahydrate (K₂B₄O₇•4H₂O) 26-35%; potassium fluoroborate (KBF₄)   26-35%; and pigment (phthalocyanine)0.1-2%.


10. The process of claim 5 further comprising the step of: combining theboric acid free flux composition with a wetting agent and boron; whereinthe composition comprises approximately by weight percent, saidcomposition added in an amount totaling 100%: water balance; wettingagent 0.1-1%; potassium bifluoride (KHF₂) 12-16%;  fumed silica (SiO₂)0.1-4%; potassium tetraborate tetrahydrate (K₂B₄O₇•4H₂O) 26-35%; potassium fluoroborate (KBF₄)   26-35%; and boron 0.1-2%.


11. A process of making a boric acid free flux composition, whichcomprises the step of: combining potassium tetraborate (K₂B₄O₇.4H₂O),potassium fluorosilicate (K₂SiF₆), and potassium fluoroborate (KBF₄).12. The process of claim 11 further comprising the step of: combiningthe boric acid free flux composition with boron; wherein the compositioncomprises approximately by weight percent, said composition added in anamount totaling 100%: potassium tetraborate tetrahydrate (K₂B₄O₇•4H₂O)44-54%;  potassium fluorosilicate (K₂SiF₆) 1-3%; potassium fluoroborate(KBF₄)  44-54%; and boron 0.1-2%. 


13. The process of claim 11 further comprising the step of: combiningthe boric acid free flux composition with a phthalocyanine pigment;wherein the composition comprises approximately by weight percent, saidcomposition added in an amount totaling 100%: potassium tetraboratetetrahydrate (K₂B₄O₇•4H₂O) 44-54%;  potassium fluorosilicate (K₂SiF₆)1-3%; potassium fluoroborate (KBF₄)  44-54%; and pigment(phthalocyanine) 0.1-2%. 